KR20200019625A - Synthetic rubber pressure sensitive adhesive, pressure sensitive adhesive sheet, and abrasive member laminate - Google Patents

Abstract

It has excellent heat resistance and substrate adhesion, and can suppress a shift and peeling even under a high temperature environment, and provides a synthetic rubber-based pressure-sensitive adhesive, an adhesive sheet, and an abrasive member laminate suitable for use in a high temperature environment. The synthetic rubber adhesive of this invention is a synthetic rubber (A) containing a styrene isoprene block copolymer, tackifying resin (B), and fatty acid ester (C) whose weight loss rate after heating at 150 degreeC for 10 minutes is 1 weight% or less. It contains. The content of the tackifying resin (B) is 5 to 60 parts by weight and the content of the fatty acid ester (C) is 0.1 to 10 parts by weight based on 100 parts by weight of the synthetic rubber (A).

Description

Synthetic rubber pressure sensitive adhesive, pressure sensitive adhesive sheet, and abrasive member laminate

The present invention relates to a synthetic rubber-based pressure-sensitive adhesive that can be suitably used for applications requiring heat resistance. Moreover, it is related with the adhesive sheet and polishing member laminated body which use the said synthetic rubber adhesive.

Since the adhesive sheet using a rubber-based adhesive can express excellent adhesive force with respect to various adherends, it is used in various industrial fields, such as an automobile use, a building material use, a home appliance use, or an abrasive member fixing use. In recent years, the use to the use which requires heat resistance is increasing. For example, in the case of an automobile use, it may be used in the place which becomes easy to become high temperature like the surroundings of a vehicle engine part besides the use in a vehicle. In addition, in the polishing member fixing application, since the polishing member is used for fixing the polishing member, it may be hot due to frictional heat during polishing or the like.

As a rubber-based adhesive, the adhesive which contains a specific amount of the styrene-isoprene-styrene (SIS) block copolymer in which a diblock amount exists in a specific range, a specific tackifying resin, and an isocyanate type crosslinking agent is disclosed (patent document 1). Moreover, the adhesive composition which consists of a base polymer which consists of a block copolymer of a monovinyl substituted aromatic compound and a conjugated diene compound, and a hydroxyl group containing 80 mgKOH / g or more of tackifying resin (TH) is disclosed (patent document 2). Further, a styrene-isoprene block copolymer (A) containing a specific amount of styrene-isoprene diblock copolymer (a1) and a specific amount of styrene-isoprene triblock copolymer (a2) and a tackifying resin having a softening point of 80 ° C or more ( The adhesive which contains tackifying resin (B) containing b1) and tackifying resin (b2) of pour point -5 degrees C or less is disclosed (patent document 3).

Moreover, the adhesive composition containing the component (C) which is at least 1 sort (s) chosen from the group which consists of a thermoplastic resin (A), a radical generator (B), a polyethylene wax, a polypropylene wax, a fatty acid amide, a fatty acid ester, and a fatty acid metal salt is disclosed. (Patent document 4).

Patent Document 1: Japanese Patent Application Laid-Open No. 2001-123140 Patent Document 2: Japanese Patent Application Laid-Open No. 2013-216853 Patent Document 3: Japanese Patent Application Laid-Open No. 2017-088702 Patent Document 4: Japanese Patent Application Laid-Open No. 2017-071726

However, since a rubber adhesive is inferior in cohesion force compared with an acrylic adhesive etc., there exists a problem that a shift | offset | difference, peeling, etc. are easy to produce at the time of use in high temperature environments, such as an automotive use and a polishing use. In addition, unlike an acrylic adhesive, most rubber adhesives do not have a process of crosslinking hardening, and since a coating film is formed by volatilizing a containing solvent at the time of coating drying, coating film formation is complete | finished at the time of completion of coating film drying. For this reason, adhesiveness with respect to a base material tends to worsen, for example, when coating a separator and volatilizing a containing solvent with a drying oven, and then transferring to a PET (polyethylene terephthalate) base material etc. after that. In particular, in a high temperature environment, problems such as the easy release of the pressure-sensitive adhesive layer from the substrate tend to occur. For this reason, the rubber type adhesive with heat resistance and base material adhesiveness which can be used in high temperature environment is calculated | required.

This invention is made | formed in view of the said background, and has excellent heat resistance and base-material adhesiveness, can suppress a shift | offset | difference, peeling, etc. even in a high temperature environment, and is suitable for use in a high temperature environment, The synthetic rubber adhesive, an adhesive sheet, and an abrasive member laminated | stacked The purpose is to provide a sieve.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said various problems, the present inventors discovered that the said subject could be solved in the following forms, and came to complete this invention.

[1]: Synthetic rubber-based pressure-sensitive adhesive containing synthetic rubber (A), tackifying resin (B), and fatty acid ester (C),

Synthetic rubber (A) contains a styrene isoprene block copolymer,

The fatty acid ester (C) has a weight loss rate of 1% by weight or less after heating at 150 ° C. for 10 minutes,

The content of the tackifying resin (B) is 5 to 60 parts by weight, and the content of the fatty acid ester (C) is 0.1 to 10 parts by weight based on 100 parts by weight of the synthetic rubber (A).

[2]: The synthetic rubber adhesive according to [1], wherein the synthetic rubber (A) contains a styrene isoprene block copolymer having a styrene content of 20 to 40% by weight and a diblock content of 15 to 70% by weight.

[3]: The synthetic rubber-based pressure sensitive adhesive according to [1] or [2], in which the tackifying resin (B) contains a terpene phenol resin having a softening point of 95 to 170 ° C.

[4]: An adhesive sheet provided with a pressure-sensitive adhesive layer formed of the synthetic rubber pressure-sensitive adhesive according to any one of [1] to [3] on one or both surfaces of the base material.

[5]: The pressure sensitive adhesive sheet according to [4], which is for fixing a polishing member.

[6]: An abrasive member laminate, in which an adhesive sheet for fixing an abrasive member according to [5] is bonded to an abrasive member and integrated.

ADVANTAGE OF THE INVENTION According to this invention, it has the outstanding heat resistance and adhesiveness of a base material, can suppress a shift | offset | difference, peeling, etc. even in a high temperature environment, and can provide the synthetic rubber adhesive, adhesive sheet, and abrasive member laminated body suitable for the use in high temperature environment. Has an excellent effect.

The synthetic rubber adhesive of this embodiment is a synthetic rubber (A) containing a styrene isoprene block copolymer, tackifying resin (B), and fatty acid ester (C) whose weight loss rate after heating at 150 degreeC for 10 minutes is 1 weight% or less. It contains. The content of the tackifying resin (B) is 5 to 60 parts by weight and the content of the fatty acid ester (C) is 0.1 to 10 parts by weight based on 100 parts by weight of the synthetic rubber (A).

The synthetic rubber adhesive of this embodiment can form an adhesive layer by coating, and can use it as an adhesive sheet provided with a base material. That is, it can be used as an adhesive sheet provided with the adhesive layer formed with the rubber-based adhesive on the single side | surface or both surfaces of a base material. Since this adhesive sheet is especially excellent in heat resistance, it can use suitably also for the automotive use used for high temperature environment, a grinding | polishing use, etc. In addition, the adhesive sheet, the adhesive tape, and the adhesive film of this embodiment are synonymous.

When using the adhesive sheet of this embodiment for automobile use, it is used for the purpose of using for fixing to automobile parts. For example, it can be used for the purpose of joining automobile interior materials, the purpose of joining the foam etc. which are used for a sealing material, etc.

When using the adhesive sheet of this embodiment for a grinding | polishing use, it can be used for joining the abrasive member laminated body integrated by bonding an adhesive sheet to the grinding | polishing member, such as a polishing pad used for the purpose of grinding | polishing, to an abrasive | polishing machine. Here, with a polishing pad, a urethane type polishing pad, a nonwoven fabric type polishing pad, a suede type polishing pad, etc. are mentioned, for example. However, what is necessary is just to be used for the grinding | polishing member for the purpose of grinding | polishing, It is not limited to these.

By improving the cohesion force of an adhesive layer and adhesiveness with respect to a base material, the synthetic rubber adhesive of this embodiment becomes difficult to generate | occur | produce a shift | offset | difference, peeling, etc. under high temperature environment. Moreover, since the adhesive sheet of this embodiment has acid resistance and alkali resistance, it can be used for fixation of either a surface side and a polishing member side. It can be used suitably as an adhesive sheet for abrasive members provided with the adhesive layer formed with the adhesive for fixing a polishing member of this embodiment on one side or both surfaces of a base material.

<< synthetic rubber adhesive >>

As described above, the synthetic rubber pressure sensitive adhesive of the present embodiment has a synthetic rubber (A), a tackifying resin (B) containing a specific copolymer, and a fatty acid having a weight loss ratio of 1% by weight or less after heating at 150 ° C for 10 minutes. Each specific amount of ester (C) is contained. Below, each is described in detail.

<Synthetic rubber (A)>

The synthetic rubber (A) of this embodiment contains at least a styrene isoprene block copolymer. By using a styrene isoprene block copolymer, it becomes possible to set it as the adhesive excellent in the adhesive performance with respect to various to-be-adhered bodies.

The styrene isoprene block copolymer may use either a linear structure or a radial structure (radial structure). Especially, when it has a linear structure, since it is a structure with high flexibility, it is excellent in adhesiveness with respect to various to-be-adhered bodies, and shows the effect which was more excellent in adhesive performance and heat resistance. Therefore, the linear structure which the styrene isoprene block copolymer consists of the triblock body (SIS) of a styrene-isoprene-styrene block, and the diblock body (SI) of styrene-isoprene is preferable.

It is preferable that diblock content in styrene isoprene block copolymer whole quantity (100 weight%) is 15 to 70 weight%, More preferably, it is 15 to 50 weight%, More preferably, 15 to 25 weight% to be. When content of a diblock body exists in 15 to 70 weight%, the fixed amount of the diblock body which does not have a styrene block body exists in the terminal, and adhesiveness with respect to a to-be-adhered body and adhesive force can be improved. Moreover, from the viewpoint of providing heat resistance by physical crosslinking of the styrene block body, the styrene content in the styrene isoprene block copolymer is preferably 20 to 40% by weight, more preferably 22 to 40% by weight. to be. By being in the range of 20-40 weight%, it can be set as the adhesive excellent in cohesion force.

As a styrene isoprene block copolymer, Quintac 3280 (made by Nippon Xeon, 25 weight% of styrene, 17 weight% of diblocks), Quintac 3270 (made by Nippon Xeon, 24 weight% of styrene, 67 weights of diblocks, for example) %), Quintac 3450 (manufactured by Nippon Zeon, 19 wt% styrene, 30 wt% diblock), Quintac 3520 (manufactured by Nippon Zeon, 15 wt% styrene, 78 wt% diblock), Quintac 3433N (Nippon xeon Company, styrene amount 16% by weight, diblock amount 56% by weight), Quintac 3421 (manufactured by Nippon Xeon, styrene amount 14% by weight, diblock amount 26% by weight), Quintac 3620 (manufactured by Nippon Xeon, styrene amount 14% by weight, Diblock amount 12% by weight), Kraton D1119 (manufactured by Kraton, 22% by weight of styrene, 66% by weight of diblock), Kraton D1126 (21% by weight of styrene, 21% by weight of diblock), Kraton D1193 (made by Kraton, 24 weight% of styrene, 20 weight% of diblock), Kraton D1117 (17 weight% of styrene, 33 weight% of diblock), Kraton D1163 (Crayton, Inc.) Styrene amount of 15 wt%, diblock amount of 38% by weight), and the like Kraton D1161 (Creighton Priest, styrene amount of 15 wt%, diblock amount of 19% by weight). It is not limited to these, Such a styrene isoprene block copolymer can be used as needed in the range which does not impair the required performance, and may be used in combination of 2 or more type.

As long as it is a range which does not impair the required performance, you may contain other synthetic rubbers other than the said specific styrene isoprene block copolymer. As other synthetic rubbers, for example, styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene rubber (SBR), polyisoprene rubber (IR), polyisobutylene (PIB), or butyl rubber (IIR) Etc. can be mentioned. When it contains synthetic rubber other than such a styrene isoprene block copolymer, it is preferable to contain 50-100 weight% of styrene isoprene block copolymers in 100 weight% of synthetic rubbers (A) from the point of balance of adhesive force and cohesion force. More preferably, it is 80-100 weight%.

In addition, as long as it is a range which does not impair the required performance, you may use together natural rubber other than a synthetic rubber (A). Although it does not specifically limit as natural rubber, What is necessary is just to knead with a kneading roller, and to adjust and use a Mooney viscosity so that it may be about 10-100, for example. Other synthetic rubbers and natural rubbers are not limited to these and can be used alone or in combination of two or more thereof.

<Adhesion imparting resin (B)>

In this embodiment, tackifying resin (B) is not specifically limited. As tackifying resin, For example, rosin-type resins, such as rosin ester, polymeric rosin, hydrogenated rosin, disproportionated rosin, maleic acid modified rosin, fumaric acid modified rosin, rosin phenol resin; terpene resins such as α-pinene resin, β-pinene resin, dipentene resin, aromatic modified terpene resin, hydrogenated terpene resin, terpene phenol resin, acid-modified terpene resin, styrene terpene resin and the like; Alkylphenol resins, coumarone resins, styrene resins, petroleum resins, and copolymers thereof, but are not limited thereto. Tackifying resin can be used 1 type or in combination of 2 or more types.

As a preferable example of tackifying resin (B), there is a terpene phenol resin. Since terpene phenol resin is excellent in compatibility with a styrene isoprene block copolymer, adhesive performance can be provided to a styrene isoprene block copolymer in a balanced manner. Moreover, since compatibility is favorable, it is hard to produce the cohesion force fall of the adhesive layer which caused the tackifying resin at the time of using, and it is possible to suppress the fall of cohesion force, and to provide adhesive performance.

As a terpene phenol resin, for example, SylVares TP95 (made by Arizona Chemical, softening point 95 ± 5 degreeC), SylVares TP105 (made by Arizona Chemical, softening point 105 ± 5 degreeC), SylVares TP115 (made by Arizona Chemical Co., softening point 115 ± 5 degreeC), for example. , YS Polyster U115 (made by Yashara Chemical Co., Ltd., softening point 115 ± 5 ° C), YS Polyster T80 (manufactured by Yashara Chemical Co., Ltd., softening point 80 ± 5 ° C), YS Polyster T100 (manufactured by Yashara Chemical Co., Ltd., softening point 100 ± 5 ° C) ), YS Polyster T115 (made by Yashara Chemical Co., Ltd., softening point 115 ± 5 ° C), YS Polyster T130 (made by Yashara Chemical Co., Ltd., softening point 130 ± 5 ° C), YS Polyster T145 (manufactured by Yashara Chemical Co., Ltd., softening point 145 ± 5) ℃) etc. can be illustrated. Terpene phenol resin is not limited to these, It can use as needed in the range which does not impair the required performance. Terpene phenol resin can be used 1 type or in combination or 2 or more types.

It is preferable that softening point is 95-170 degreeC of tackifying resin (B). By making the softening point of tackifying resin into the said range, the fall of the cohesion force resulting from tackifying resin is suppressed, and heat resistance improves. As for a softening point from the said viewpoint, 110-150 degreeC is more preferable.

Content of tackifying resin (B) is 5-60 weight part with respect to 100 weight part of synthetic rubbers (A). By setting it as said range, the balance of adhesion performance and cohesion force is easy to be obtained, the fall of cohesion force resulting from tackifying resin can be suppressed, and heat resistance can be improved. From said viewpoint, 10-50 weight part is more preferable. Especially preferably, 10-25 weight part is more preferable from a viewpoint of cohesion force.

<Fatty acid ester (C)>

In this embodiment, the fatty acid ester (C) can use the well-known compound which satisfy | fills the characteristic that the weight reduction rate after heating at 150 degreeC for 10 minutes is 1 weight% or less. Synthetic rubber-based pressure-sensitive adhesive of the present embodiment, in order to impart heat resistance, the amount of tackifying resin is 5 to 60 parts by weight as described above, but if the amount of tackifying resin (B) is small, synthetic rubber-based pressure-sensitive adhesive, There is no viscosity and it tends to reduce adhesive force and adhesiveness. However, this problem can be solved by using together with a fixed amount of the self-release acid ester (C). That is, by using together a specific amount of tackifying resin (B) and a specific amount of fatty acid ester (C), it becomes possible to provide moderate flexibility to a coating film, and can provide adhesiveness without reducing heat resistance. However, in the fatty acid ester with low volatility, a fatty acid ester volatilizes at the time of drying, and the required adhesive improvement effect is not acquired. In addition, when dried using a coater or the like to form an adhesive sheet, problems such as volatilized fatty acid esters adhere to the coater oven and contaminate the coater. For this reason, it is necessary to use fatty acid ester whose weight reduction rate after heating at 150 degreeC for 10 minutes is 1 weight% or less. By using the fatty acid ester (C) of this embodiment, the outstanding effect which improves not only contaminant but also base-material adhesiveness can be exhibited. The weight reduction rate after heating for 10 minutes at 150 degreeC becomes like this. More preferably, it is 0.5 weight% or less.

Content of fatty acid ester (C) shall be 0.1-10 weight part with respect to 100 weight part of synthetic rubbers (A). By setting it as the said range, base material adhesiveness can be improved. From said viewpoint, 0.3-8 weight part is more preferable.

The fatty acid ester (C) improves the fingertip viscosity on the surface of the coating film in terms of providing flexibility to the coating film. However, since fatty acid ester volatilizes during storage of an adhesive sheet, there exists a tendency for the fingertip viscosity of a coating film surface to fall. Therefore, the monoester type fatty acid which has a high polarity ester bond is less than 1 weight% after heating for 10 minutes at 150 degreeC which shows that the fingertip viscosity is hard to fall and shows the favorable substrate adhesiveness also in a substrate adhesiveness test. Preference is given to using esters or diester fatty acid esters. From the viewpoint of fingertip viscosity, diester fatty acid esters are more preferred.

<Hardener>

In this embodiment, a hardening | curing agent can be used as needed. Depending on the application, although a number required from high adhesive force to low adhesive force is various, it is possible to add a curing agent for the purpose of controlling the adhesive force. As a hardening | curing agent, an isocyanate compound, an aziridine compound, a metal chelate compound, an epoxy compound, etc. can be used as needed in the range which does not impair the required performance. You may use a hardening | curing agent individually or in combination of 2 or more types.

As an isocyanate compound, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethyl, for example. And polyisocyanate compounds such as xylylene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate and polymethylene polyphenyl isocyanate. Moreover, the adduct, biuret, and isocyanurate body of these isocyanate compounds and polyol compounds, such as a trimethylol propane, can also be illustrated. Moreover, adducts, such as these isocyanate compounds, well-known polyether polyol, polyester polyol, acryl polyol, polybutadiene polyol, polyisoprene polyol, etc. are mentioned. As an isocyanate compound, it is preferably an adduct of tolylene diisocyanate trimethylol propane.

Examples of the aziridine compound include N, N'-hexamethylene-1,6-bis (1-aziridinecarboxyamide, trimethylolpropane-tri-β-aziridinylpropionate, N, N'- Diphenylmethane 4,4'-bis (1-aziridinecarboxyamide), trimethylolpropane-tri-β- (2-methylaziridine) propionate, and the like.

As a metal chelate compound, a metal complex compound can be used, for example. Examples of the metal include nickel, aluminum, chromium, iron, titanium, zinc, cobalt, manganese, copper, tin and zirconium. Examples of the metal chelate compound include ferric trisacetylacetonate, aluminum trisacetylacetonate, aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tris (ethylacetoacetate), and the like. More preferred is aluminum trisacetylacetonate.

Examples of the epoxy compound include bisphenol A, an epoxy resin of epichlorohydrin type, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1, 6-hexanediolglycidylether, trimethylolpropanetriglycidylether, diglycidylaniline, diamineglycidylamine, N, N, N ', N'-tetraglycidyl-m-xylylenediamine and 1, 3-bis (N, N'- diamine glycidyl aminomethyl) cyclohexane, etc. are mentioned.

<Anti-aging agent>

In this embodiment, an anti-aging agent can be used as needed. Anti-aging agent is used for the purpose of preventing deterioration of a rubber component. As such an anti-aging agent, For example, Nonflex WS (made by Seiko Kagaku Corporation, anti-aging agent), Nonflex WS-P (made by Seiko Kagaku Corporation, anti-aging agent), Nonflex MBP (made by Seiko Kagaku Corporation, anti-aging agent), Nonflex CBP (made by Seiko Kagaku Corporation, anti-aging agent), Nonflex EBP (made by Seiko Kagaku Corporation, anti-aging agent), Nonflex TNP (made by Seiko Kagaku Corporation, anti-aging agent), Nonflex MB (made by Seiko Kagaku Corporation, anti-aging agent) ), Non-flex RD (made by Seiko Kagaku Corporation, anti-aging agent), non-flex OS (made by Seiko Kagaku Corporation, anti-aging agent), and non-flex DCD (made by Seiko Kagaku Corporation, anti-aging agent) can be illustrated. However, it should just be an anti-aging agent, It is not limited to these. Such anti-aging agent can be used as needed in the range which does not impair the required performance, and can be used 1 type or in combination of 2 or more types.

In the present embodiment, the anti-aging agent is used for the purpose of preventing deterioration due to oxidation or the like, or for the purpose of preventing deterioration due to heat, and the like. An antioxidant, an antioxidant deterioration agent, and a heat deterioration inhibitor are synonymous. to be.

<Other additives>

The synthetic rubber adhesive of this embodiment may contain various additives, such as a filler, a pigment, dye, a diluent, a polymerization inhibitor, a ultraviolet absorber, an ultraviolet stabilizer, a coupling agent, etc. mix | blended with a well-known adhesive as needed. In addition, these additives are used 1 type or in combination of 2 or more types. In addition, what is necessary is just to make the addition amount of an additive into the quantity from which required physical properties are obtained, and it is not specifically limited.

<< adhesion sheet >>

The adhesive sheet of this embodiment is equipped with the adhesive layer formed with the rubber adhesive of this embodiment on the single side | surface or both surfaces of a base material. 5-150 micrometers is preferable and, as for the thickness of an adhesive layer, 10-100 micrometers is more preferable. By setting an adhesive layer in the range of 5-150 micrometers, the adhesive tape excellent in adhesive performance and heat resistance can be obtained.

Coating of an adhesive can use well-known methods, such as the roll coater method, the comma coater method, the lip coater method, the die coater method, the reverse coater method, the silk screen method, and the gravure coater method, for example. The coater can be dried by a hot air oven, an infrared heater, or the like.

As a base material, the member which can use a nonwoven fabric, paper, a plastic film, synthetic paper, etc. can be used. When using as a base material (core material) of an adhesive sheet, a nonwoven fabric and a plastic film are preferable. The plastic film is, for example, polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, PPS (polyphenylene sulfide), nylon, triacetyl cellulose, cycloolefin, polyimide and polyamide, and the like. You can say what you did.

The base material may be an optical member such as an antireflection (AR) film, a polarizing plate, a retardation plate, and the like coated on the plastic film with a desired coating solution, for example. Moreover, in order to improve adhesiveness with an adhesive layer, a base material may perform an easily adhesive process. The said easily bonding process can use well-known methods, such as the dry method which performs corona discharge, and the wet method which coats with an anchor coat agent.

The substrate may be a substrate having an antistatic layer on which an antistatic layer is formed. In addition to using an antistatic agent, the antistatic layer is preferably formed of a composition in which at least one of conductive carbon particles, conductive metal particles, conductive polymers, and the like is added, and blended with a resin. Moreover, it is good also as a base material with an antistatic layer by performing metal vapor deposition or metal plating on a surface. Although the thickness in particular of the base material of this embodiment is not restrict | limited, 5-300 micrometers is preferable. It is more preferable to use the film in which the easily bonding process etc. are not given in the said base material. In the case of the rubber-based pressure sensitive adhesive, since the pressure-sensitive adhesive is easily peeled from the base material when the easy adhesion treatment for corona discharge is performed, it is preferable to apply the rubber pressure sensitive adhesive to the surface on which the easy adhesion treatment for corona discharge is not performed.

The adhesive sheet can provide the peeling liner which protects an adhesive layer until just before use on an adhesive layer as needed. The peeling liner at the time of producing an adhesive sheet has a peeling layer formed by coating a peeling agent on base materials, such as a paper, a plastic film, and synthetic paper, for example. Examples of the release agent include silicone, alkyd resin, melamine resin, fluorine resin, and acrylic resin. Moreover, the thickness of a peeling liner does not have a restriction | limiting in particular, About 10-200 micrometers.

EXAMPLE

Although an Example demonstrates this invention more concretely below, this invention is not limited to a following example. In addition, in an example, "part" shall mean "weight part" and "%" shall mean "weight%."

In addition, the softening point of tackifying resin and the measuring method of the volatility of fatty acid ester are as follows.

<Softening point of adhesion grant resin>

It measured according to JISK5902 and JISK2207.

Volatile Fatty Acid Ester

The volatility of the fatty acid esters was measured in the following order. First, a menth can with a can lid (manufactured by Edogawa Seikan Co., Ltd., with a circular can cover diameter 46 mm x height 15 mm lid) (hereinafter referred to as a mentor can) is weight (X), and then a sample is placed in a mentor can with a can lid. About 2 g of was added and the menth can containing the sample was made into the weight (Y). Next, open the lid of the metal can containing the sample, heat it at 150 ° C. for 10 minutes, take out the mentum can, immediately close the lid, allow it to cool at room temperature, and then cool the men with the can lid containing the sample after heating. The tumble can was made into weight Z.

The weight reduction rate after heating at 150 degreeC for 10 minutes was computed using the following formula (1).

(Formula 1) Weight reduction rate (%) = 100-((Z-X) / (Y-X)) × 100

Example 1

(Rubber type adhesive 1)

In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen inlet tube, 100 parts by weight of Creton, D1119, as a synthetic rubber, and methyl ethyl ketone and toluene were added as appropriate in a nitrogen atmosphere. Subsequently, the flask was gradually heated and heating was continued at an internal temperature of about 50 ° C. for 3 hours. After completion of heating, the mixture was cooled and 25 parts by weight of YS Polyster T115 (manufactured by Yashara Chemical Co., Ltd.) and fatty acid ester was used as tackifying resin at internal temperature of about 40 ° C. or less, and Unister MB-1381 (manufactured by Nichiyu Corp.) 2 parts by weight, 2 parts by weight of non-plex EBP (manufactured by Seiko Kagaku Co., Ltd.) as an anti-aging agent was diluted with methyl ethyl ketone and toluene, and stirring was continued until the tackifying resin was dissolved. A rubber adhesive solution (adhesive 1) having a viscosity of 1500 mPa · s was obtained.

Examples 2 to 26 and Comparative Examples 1 to 7

(Rubber-based adhesive 2-33)

Except having changed the kind and compounding quantity (non-volatile content weight part) of synthetic rubber, tackifying resin, and fatty acid ester as described in Tables 1-3, it is the same as adhesive 1 of Example 1, and it is a rubber type adhesive (adhesive 2 ~ 33) was obtained.

TABLE 1

TABLE 2

TABLE 3

The symbol in Tables 1-3 is as follows. In addition, a compounding quantity is the addition amount (weight part) of non volatile matter conversion with respect to solid content of synthetic rubber.

<Synthetic rubber: Styrene isoprene block copolymer (% by weight)>

Kraton D1119

(Product made from Kraton, 22 weight% of styrene, 66 weight% of diblocks, linear structure)

Quintac 3270

(Nippon Xeon company, styrene amount 24 weight%, diblock amount 67 weight%, linear structure)

Kraton D1161

(Product made from Crayton, styrene amount 15 weight%, diblock amount 19 weight%, linear structure)

Quintac 3620

(Nippon Xeon company make, styrene amount 14 weight%, diblock amount 12 weight%, linear structure)

<Adhesion grant resin>

YS Polyster T115

(Yashara Chemical Co., Ltd., terpene phenol resin, softening point 115 degreeC)

YS Polyster T130

(Made by Yashara Chemical Corporation, terpene phenol resin, softening point 130 degreeC)

YS Polyster T100

(Yashara Chemical Co., Ltd., terpene phenol resin, softening point 100 degrees Celsius)

YS Polyster T80

(Yashara Chemical Co., Ltd., terpene phenol resin, softening point 80 degreeC)

Pencel D125

(Made by Arakawa Kagaku Corporation, rosin ester resin, softening point 125 degrees Celsius)

<Fatty acid ester>

Unister MB-1381 (manufactured by Nichi Corporation, Monoester, 0.1% by weight reduction)

Unister HP-281R (manufactured by Nichi Corporation, diester, weight reduction rate 0.1%)

Unister HR-20B (manufactured by Nichi Corporation, diester, weight loss rate 0.1%)

Unister M-182A (manufactured by Nichi Corporation, monoester, weight loss rate 4.5%)

Unister H-208BRS (manufactured by Nichi Corporation, Diester, 3.5% by weight reduction)

<Additive>

Nonflex EBP (manufactured by Seiko Kagaku Corporation, anti-aging agent)

<Evaluation of the adhesive sheet>

The adhesive sheet was formed using the obtained rubber-based adhesive agent, and the following method evaluated. The evaluation results are shown in Tables 4-8.

(Production of the adhesion sheet)

The adhesive sheet which the 1st peeling liner, the 1st adhesive layer, the base material, the 2nd adhesive layer, and the 2nd peeling liner laminated in this order was produced. Specifically, as shown in Tables 4 to 8, the obtained rubber-based pressure-sensitive adhesive was coated on a 25-μm first release liner so that the thickness after drying was 40 μm, and the first pressure-sensitive adhesive layer was obtained by drying at 100 ° C. for 10 minutes. Then, the 1st adhesive layer and the PET film base material were bonded together. Next, the obtained rubber-based adhesive was coated on the second release liner so that the thickness after drying was 30 μm, and the second pressure-sensitive adhesive layer was obtained by drying at 100 ° C. for 10 minutes. And the adhesive sheet was obtained by bonding a 2nd adhesive layer to the PET film base surface on which the 1st adhesive layer is not bonded, and leaving it to stand at 23 degreeC-50% for 1 week.

(adhesiveness)

The 2nd peeling liner of the obtained adhesive sheet was peeled, and the exposed 2nd adhesive layer and 25 micrometers PET film were bonded together. And it was set as the magnitude | size of width 25mm x length 100mm, and this was made into the sample. Subsequently, under 23 ° C.-50% RH atmosphere, the first release liner was peeled off, and the exposed first pressure sensitive adhesive layer was subjected to a roller of 2 kg on a stainless steel plate (adhesive force to SUS) or a polypropylene plate (adhesive force to PP). One reciprocation was crimped. And the obtained sample was left to stand for 20 minutes or 24 hours. Subsequently, each sample was subjected to the adhesive force of the first pressure-sensitive adhesive layer under conditions of a peel angle of 180 degrees and a peel rate of 0.3 m / min using a tensile tester in accordance with the measuring method of JISZ1528 under an atmosphere of 23 ° C.-50% RH. Was measured. In the same manner, the adhesive force of the second pressure sensitive adhesive layer was measured.

(retention)

The 2nd peeling liner of the obtained adhesive sheet was peeled, and the exposed 2nd adhesive layer and 25 micrometers PET film were bonded together. And it was set as the magnitude | size of width 25mm x length 100mm, and this was made into the sample. Subsequently, under 23 ° C.-50% RH atmosphere, the first peeling liner was peeled off by 25 mm in length × 25 mm in width, and the exposed first pressure-sensitive adhesive layer was reciprocally crimped once with a 2 kg roll on a stainless steel plate, It was left to stand for 20 minutes in the atmosphere of RH. Then, it weighed 1 kg of weights in 80 degreeC atmosphere, and set it so that a force might be applied in 180 degree | times, and it measured after how many millimeters the adhesive sheet shifted from an adherend after 24 hours. In addition, when the adhesive sheet completely shifted away from the adherend, the number of seconds of falling was measured. In the same manner, the holding force of the second pressure sensitive adhesive layer was measured.

(Acid resistance)

The 2nd peeling liner of the obtained adhesive sheet was peeled, and the exposed 2nd adhesive layer and 25 micrometers PET film were bonded together. And it was set as the magnitude | size of width 25mm x length 100mm, and this was made into the sample. Subsequently, in 23 degreeC-50% RH atmosphere, a 1st peeling liner is peeled off and the exposed 1st adhesive layer is reciprocally crimped once with a roller of 2 kg on a stainless steel plate (adhesive force to SUS), and 23 degreeC-50 It was left for 24 hours in an atmosphere of% RH. Then, it was immersed in the aqueous solution adjusted to pH 1.5 using sulfuric acid, and left to stand for 24 hours in 40 degreeC environment. Then, the sample was taken out from aqueous solution and left to stand for 1 hour in the atmosphere of 23 degreeC-50% RH after water washing. Then, in 23 degreeC-50% RH atmosphere, adhesive force was measured at the peeling rate of 300 mm / min using the tension test based on the measuring method of JISZ1528. Adhesive force with the stainless steel plate measured in the evaluation of the above-mentioned "adhesive force" (adhesive force of 180 degrees of peeling angle after leaving the stainless steel plate and the crimped | bonded sample for 24 hours (hereinafter, "adhesive force after 180 degrees to 180 degrees with respect to a stainless steel plate") It can be said that the smaller the difference with the value of))), the better the acid resistance.

 Adhesion difference = (adhesion after immersion of pH 1.5 aqueous solution)-(adhesion after 180 degrees to stainless steel plate)

In the same manner, the acid resistance of the second pressure sensitive adhesive layer was measured.

(Alkali resistance)

The 2nd peeling liner of the obtained adhesive sheet was peeled, and the exposed 2nd adhesive layer and 25 micrometers PET film were bonded together. And it was set as the magnitude | size of width 25mm x length 100mm, and this was made into the sample. Subsequently, under a 23 ° C.-50% RH atmosphere, the first release liner was peeled off, and the exposed first pressure sensitive adhesive layer was reciprocally pressed once with a roller of 2 kg on a stainless steel plate (adhesive force to SUS), and then 23 ° C.-50 ° C. By leaving to stand for 20 minutes in the atmosphere of% RH, the exposed 1st adhesive layer was affixed on the stainless steel plate, and was left to stand for 24 hours in the atmosphere of 23 degreeC-50% RH. Then, it was immersed in the aqueous solution adjusted to pH 11.5 using sodium hydroxide, and was left to stand for 24 hours in 40 degreeC environment. Thereafter, the sample was taken out from the aqueous solution, washed with water, and left to stand in an atmosphere of 23 ° C.-50% RH for 1 hour. Then, in 23 degreeC-50% RH atmosphere, adhesive force was measured at the peeling rate of 300 mm / min using the tension test based on the measuring method of JISZ1528. It can be said that alkali resistance is excellent, so that the difference with the value of the adhesive force after 180 degree | time 24 hours with respect to the stainless steel plate measured in evaluation of the "adhesive force" mentioned above is small.

Adhesion difference = (adhesion after immersion of aqueous solution of pH 11.5)-(adhesion after 180 degrees to stainless steel plate)

In the same manner, the alkali resistance of the second pressure sensitive adhesive layer was measured.

(Substrate adhesion)

The 2nd peeling liner of the obtained adhesive sheet was peeled off, and the exposed 2nd adhesive layer and 25 micrometers PET film base materials were bonded together. And two samples cut | disconnected in the magnitude | size of width 25mm x length 100mm were prepared, and these were made into the measurement sample. Subsequently, in 23 degreeC-50% RH atmosphere, the 1st peeling liner was peeled from two obtained samples, the exposed 1st adhesive layer surfaces were bonded together, reciprocally crimped once with a 2 kg roller, and left to stand for 20 minutes. . And it measured on the conditions of 90 degree of peeling angles, and the peeling speed of 0.3 m / min using the tensile tester.

E: Peeling of the adhesive layer did not occur from the base material (good).

G: The adhesive layer peeled slightly from the base material (peeling is less than 30% when the bonding surface is set to 100).

NG: The adhesive layer almost peeled from the base material (30% or more when the bonding surface is set to 100). (Not practical)

(Pollutant)

The obtained adhesive was 100m coated at a coating width of 200 mm, a temperature of 130 ° C., and a coating rate of 0.5 m / min so that the thickness after drying was 50 µm using a test coater. After the completion of the coating, the glass windows installed to observe the inside of the drying oven were observed to evaluate the contamination based on the volatilization of fatty acid esters depending on the presence or absence of fogging.

E: No fogging occurred (good).

NG: fogging occurred (not practical).

(Finish fingertip viscosity)

The obtained adhesive sheet was left to stand in a 40 degreeC oven for 1 week, and then taken out, and it was left to stand in 23 degreeC-50% RH atmosphere for 24 hours (sample 1). A part of the peeling liner of the 2nd surface of the sample 1 left to stand for 24 hours was peeled off, and the fingertip viscosity of the exposed adhesive layer surface was measured. Thereafter, the same sample was left for 3 weeks in an oven at 40 ° C. (for 1 month in total), and then taken out, and left for 24 hours under 23 ° C.-50% RH atmosphere (Sample 2). A part of the peeling liner of the second surface of Sample 2 that was left to stand for 24 hours was peeled off, and the fingertip viscosity of the exposed pressure-sensitive adhesive layer surface was determined, and the comparative evaluation was performed with the fingertip viscosity after one week.

E: No change compared to a week after curing (good)

G: slightly lower than a week after curing (the practical range)

NG: significantly lower than one week after curing (not practical)

TABLE 4

TABLE 5

TABLE 6

TABLE 7

TABLE 8

As shown in Table 4-Table 8, the double-sided adhesive tape of this Example has the weight reduction rate after 10 minutes of heating at synthetic rubber (A), tackifying resin (B), and 150 degreeC containing a styrene isoprene block copolymer. The fatty acid ester (C) which is 1 weight% or less is contained, and content of tackifying resin (B) is 5-60 weight part and content of fatty acid ester (C) with respect to 100 weight part of synthetic rubbers (A). By using 10 parts by weight, it is difficult to cause misalignment or peeling even under a high temperature environment, and it is possible to improve the adhesion to the substrate, and it is difficult to peel off the adhesive layer from the substrate, so that it can be confirmed that it can be used under a high temperature environment than before. there was.

In particular, when the styrene isoprene block copolymer has a diblock content of 15 to 70% by weight and a styrene content of 20 to 40% by weight in the total amount of the styrene isoprene block copolymer (100% by weight), the adhesion and cohesion are particularly excellent. did. Moreover, when tackifying resin (B) was terpene phenol resin and the softening point was 95-170 degreeC, cohesion force was especially excellent.

[Industrial availability]

The synthetic rubber-based adhesive agent according to the present invention can be applied to the overall adhesive use for the adherend. For example, it is suitable for joining parts, and can be used as an adhesive sheet in various industrial fields including automobiles, abrasive member fixings, building materials, home appliances, and the like.

This application claims the priority based on Japanese Patent Application No. 2017-105737 for which it applied on May 29, 2017, and introduces all the indication here.

Claims (6)

As a synthetic rubber adhesive containing synthetic rubber (A), tackifying resin (B), and fatty acid ester (C),
The said synthetic rubber (A) contains a styrene isoprene block copolymer,
The said fatty acid ester (C) is 1 weight% or less in weight loss rate after heating at 150 degreeC for 10 minutes,
The content of the tackifying resin (B) is 5 to 60 parts by weight, and the content of the fatty acid ester (C) is 0.1 to 10 parts by weight based on 100 parts by weight of the synthetic rubber (A). The synthetic rubber pressure sensitive adhesive according to claim 1, wherein the synthetic rubber (A) contains a styrene isoprene block copolymer having a styrene content of 20 to 40% by weight and a diblock content of 15 to 70% by weight. The synthetic rubber-based pressure sensitive adhesive according to claim 1 or 2, wherein the tackifying resin (B) contains a terpene phenol resin having a softening point of 95 to 170 ° C. The adhesive sheet which was provided with the adhesive layer formed from the synthetic rubber adhesive in any one of Claims 1-3 on the single side | surface or both surfaces of a base material. The adhesive sheet according to claim 4, which is for fixing an abrasive member. The abrasive member fixing adhesive sheet of Claim 5 is bonded to an abrasive | polishing member, and integrated, The abrasive | polishing member laminated body characterized by the above-mentioned.